Five Energetic Cocrystals of BTF by Intermolecular Hydrogen Bond and π‑Stacking Interactions

• Published in: Crystal growth & design 2013-02, Vol.13 (2), p.679-687
• Main Authors: Zhang, Haobin, Guo, Changyan, Wang, Xiaochuan, Xu, Jinjiang, He, Xuan, Liu, Yu, Liu, Xiaofeng, Huang, Hui, Sun, Jie
• Format: Article
• Language: English
• Subjects: Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Equations of state, phase equilibria, and phase transitions; Exact sciences and technology; Materials science; Methods of crystal growth; physics of crystal growth; Physics; Solid-solid transitions; Specific phase transitions; Structure of solids and liquids; crystallography; Structure of specific crystalline solids
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/cg301353f

Five novel BTF (benzotrifuroxan) cocrystals, possessing a similar density to RDX (1,3,5-trinitrohexahydro-1,3,5-triazine), have been prepared and reported first. Their single-crystal structures are presented and discussed. Interactions between cocrystal formers are discussed with shifts in the IR spectra providing additional support for the presence of various interactions. Hydrogen-bonding and π-stacking interactions are found to be the most prominent. Especially, the interactions between electron-poor π-systems of BTF and electron-rich groups of other cocrystal formers such as nitro groups of TNB exist commonly in all five novel cocrystals. This kind of interaction can be a more potential driving force for energetic cocrystals, since explosives with poor active hydrogen bonds are usually hard to form cocrystals with other explosives for the lack of strong intermolecular interactions. Because of the changes in structure, the physicochemical characteristics including density and melting point together with energetic properties of BTF altered after cocrystallization. All of the densities are between both of the cocrystal formers. Cocrystals of BTF with TNT and TNB have impact sensitivities between those of both cocrystal formers, while the remaining three cocrystals (BTF/TNA, BTF/MATNB, and BTF/TNAZ) all are more sensitive than either cocrystal former. It indicates that a cocrystal with TNT or TNB can reduce the shock sensitivity of BTF; especially, the cocrystal BTF/TNB not only has a lower sensitivity than RDX but also equal energetic properties, which potentially improve the viability of BTF in explosive applications. This paper owns an important consideration in the design of future BTF and other explosive cocrystals, and the result provides some feasibility to improve the application of the high explosive BTF.